(a) Field of the Invention
This invention relates to the field of chemistry and more particularly to novel acid addition salts of poly(N-substituted sulfonamido) phthalocyanines useful as direct dyes, particularly in the dyeing of cellulose; to storage-stable concentrated aqueous dye compositions prepared therefrom; and to processes for preparing said phthalocyanines, said acid addition salts and said storage-stable concentrated aqueous dye solutions.
(b) Description of the Prior Art
A class of organic compounds known as direct dyes are known to be useful as dyeing agents for paper and fabrics. Among this group of organic compounds there are named phthalocyanines and their acid addition salts. However, heretofore know phthalocyanines and their known acid addition salts have suffered from a number of deficiencies when employed as dyes for coloring cellulose in the form of bleached pulp of the type used for the manufacture of household paper goods such as paper napkins, paper toweling, facial tissues and so forth. Thus, they have been found to undesirably bleed out of paper products colored with them when the article is brought into contact with common household solutions, for example, water, milk, soapy solutions, detergent solutions, alcoholic beverages, vinegar, rubbing alcohol and so forth. They have also been found to have relatively poor substantivity to bleached pulp and have suffered from a low rate and degree of exhaust from dyeing solutions containing them. They have also been found to have a relatively poor degree of color discharge when bleached with hypochlorite or "chlorine" bleach. There is thus a need for water-soluble phthalocyanine dyestuffs for coloring bleached pulp which have a high bleed resistance, good substantivity, a high rate and a high degree of exhaust from aqueous dyeing solutions in which they are utilized, and a high degree of color discharge when bleached with hypochlorite or "chlorine" bleach.
The following items to date appear to constitute the most relevant prior art with regard to the instant invention.
U.S. Pat. No. 4,069,064 (issued Jan. 17, 1978) discloses a phthalocyanine formulation which is stabilized against recrystallization and change of modification and which contains as the stabilizer a salt or the corresponding homogeneous mixture, of (.alpha.) one or more phthalocyanine derivatives of the formula Pc[--X--NR.sup.1 R.sup.2 ].sub.n, where Pc is an n-valent radical of the metal-free phthalocyanine, of a copper phthalocyanine or of a mixture of these, X is --CH.sub.2 --,SO.sub.2 --NR--alk--, --CH.sub.2 --COO--C.sub.2 H.sub.4 -- or --CH.sub.2 --CH.sub.2 --COO--C.sub.3 H.sub.6 --, R.sup.1 is hydrogen, alkyl of 1 to 20 carbon atoms, phenyl, phenyl which is substituted by methyl, methoxy, ethoxy or chlorine, --(C.sub.2 H.sub.4 --NH).sub.z H or --(C.sub.3 H.sub.6 --NH).sub.z H, R.sup.2 is hydrogen, alkyl of 1 to 6 carbon atoms or cycloalkyl of 6 to 8 carbon atoms, alk is linear or branched saturated alkylene of 2 to 6 carbon atoms, R is hydrogen or alkyl of 1 to 4 carbon atoms, and R and R.sup.2 may be linked to one another, n is a number from 2 to 5, z is an integer from 1 to 3 and the group --NR.sup.1 R.sup.2 may also be a heterocyclic ring selected from the group consisting of morpholinyl, thiomorpholinyl, piperazinyl, N-methylpiperazinyl, N-ethylpiperazinyl, piperidinyl, pyrrolidinyl and ##STR1## and (.beta.) a saturated or unsaturated aliphatic sulfonic acid of 8 to 20 carbon atoms, a benzenesulfonic or naphthalenesulfonic acid, substituted by one or two alkyl groups each of 6 to 20 carbon atoms, and in which the benzene or naphthalene nucleus can be substituted by a hydroxyl group, or mixtures thereof, the molar ratio of (.alpha.):(.beta.) being from 1:1 to 1:5, and the said salt or corresponding mixture acting as a stabilizer in the formulation.
U.S. Pat. No. 2,863,875 (issued Dec. 9, 1958) discloses a phthalocyanine dyestuff containing the group [--SO.sub.2 N(R.sub.1)R.sub.2 (NR.sub.3 R.sub.4)].sub.n wherein R.sub.1 is a hydrogen or a lower alkyl, R.sub.2 is a lower alkylene, R.sub.3 and R.sub.4 are lower alkyl or hydroxy lower alkyl and n is one to eight.
U.S. Pat. No. 4,036,585 (issued July 17, 1977) discloses a copper phthalocyanine dyestuff bearing the groups [--SO.sub.2 NHCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 CN].sub.n wherein n is 3 to 4.
U.S. Pat. No. 3,053,849 (issued Sept. 11, 1962) discloses phthalocyanine dyestuffs of the formula ##STR2## wherein Pc is a phthalocyanine; L is [--NH(CHR.sub.3 CH.sub.2 Y).sub.m --CHR.sub.4 CHR.sub.5 X]; R.sub.3, R.sub.4 and R.sub.5 are hydrogen or alkyl; Y is --NH--, --N--lower alkylene, --O-- or --S--; m is 0 or 1; X is Cl, Br, sulfo or sulfonyloxy; M is amino or substituted amino; a is 0-2; b is 1-3; and C is 1-3 provided that the sum of a+b+c does not exceed four.
U.S. Pat. No. 3,057,873 (issued Oct. 9, 1962) discloses phthalocyanine dyestuffs of the formula [(X.sub.1 SO.sub.2).sub.m --Pc--(SO.sub.3.sup..crclbar.).sub.n ][X.sub.2.sup..sym. ].sub.n wherein Pc is a phthalocyanine radical; X.sub.1 is a polyalkylene polyamine containing at least one lipophilic radical and at least three basic nitrogen atoms; X.sub.2 is the ammonium cation of such a polyalkylene polyamine; and m+n is 2 to 4.
German Offenlegenschrift No. 2,629,675 (published Jan. 20, 1977), which corresponds to U.S. Pat. No. 4,111,650 (issued Sept. 5, 1978), discloses a stable concentrated liquid preparation of a paper dye of the copper phthalocyanine class which preparation contains 15 to 50 percent by weight of the dye of the formula CuPc[SO.sub.2 NH(CH.sub.2).sub.3 N(CH.sub.2).sub.3 ].sub.2 to 3 [SO.sub.3 H].sub.1 to 2 wherein CuPc represents copper phthalocyanine, or the alkali salt thereof, dissolved in 30 to 65 percent by weight of water, 5 to 15 percent by weight of N-methylpyrrolidone, 1 to 7 percent water by weight of benzyl alcohol, and 1 to 5 percent by weight of a lower aliphatic carboxylic acid.